TW200937450A - Conductive compositions and processes for use in the manufacture of semiconductor devices: flux materials - Google Patents

Abstract

Described herein are a silicon semiconductor device and a conductive paste, including a flux material, for use in the front side of a solar cell device.

Description

200937450 IX. Description of the Invention: TECHNICAL FIELD Embodiments of the present invention relate to a germanium semiconductor device, and a conductor silver paste for the front side of a solar cell device. [Prior Art] A conventional solar cell structure having a p-type substrate has a negative electrode which is usually located on the front side or the sun surface of the battery, and a positive electrode located on the back side. It is well known that radiation of the appropriate wavelength falling on the p-n junction of the semiconductor body acts as a source of external energy that creates a hole-electron pair in the body. Since there is a potential difference at the p_n junction, the holes and electrons move in the opposite direction through the junction and thereby cause a current flow that can transfer power to the external circuit. Most solar cells are in the form of germanium wafers that have been metallized, that is, have conductive metal contacts. Despite the various methods and compositions for forming solar cells, there is a need for compositions, structures and devices and methods of manufacture having improved electrical performance. • SUMMARY OF THE INVENTION One embodiment of the invention relates to a structure comprising: a '〇) thick film composition comprising: • a) conductive silver; b) — or a plurality of fluxing materials; dispersed in e) (b) - or a plurality of insulating films; wherein the thick film composition is formed on one or more insulating media, and wherein the one or more insulating media are thick after firing at 135568.doc 200937450 The components of the film composition penetrate and remove the organic medium. In an embodiment, the flux material comprises one or more glass frits. In one aspect of this embodiment, the structure further comprises one or more semiconductor substrates. In another aspect, the insulating films are formed on the one or more semiconductor substrates. One aspect of the invention pertains to a semiconductor device incorporating the structure. Another aspect relates to a semiconductor device comprising the structure, wherein the composition has been fired, wherein the firing removes the organic vehicle and sinters the silver and flux material, and wherein the conductor silver and the glass frit mixture penetrates the insulation membrane. Another aspect relates to a solar cell comprising the structure. In one aspect of this embodiment, the thick film composition further comprises an additive. In another aspect, the additive is selected from the group consisting of: (a) a metal, wherein the metal is selected from the group consisting of Zn, Mg, Gd, Ce, Zr, Ti, Mn, Sn, Ru, Co,

Fe, Cu and Cr; (b) selected from the group consisting of Zn, Mg, Gd, Ce, Zr, Ti, Mn,

a metal oxide of one or more of the metals of Sn, RU, Co, Fe, Cu, and Cr; (c) any compound of a metal oxide that can be produced after firing; and (d) a mixture thereof In an embodiment, the additive is Zn or MgO. In one aspect of the embodiment, the glass frit comprises: 2〇3, B2〇3, 8-25% by weight of the glass frit, and further comprising one or more components selected from the group consisting of the following: :Si〇2, P2〇5, Ge〇2& v2o5 In one aspect of the 6-fold embodiment, the insulating film contains one or more components selected from the group consisting of titanium oxide, tantalum nitride, and SiNx: H, cerium oxide and cerium oxide / 135568.doc 200937450 titanium oxide. In one aspect of this embodiment, the structure is suitable for use in the manufacture of photovoltaic devices. In one aspect of this embodiment, the glass frit comprises a component selected from the group consisting of: (4) a metal, wherein the metal is selected from the group consisting of Zn, &, ^, a, • ΖΓ, Τ, Mn, Sn, RU, C〇, Fe, Cu, and Cr; (8) a metal oxide selected from the group consisting of Zn, Mg, Gd, Ce, Zr, Ti, Mn, Sn, Ru, c〇, FeCuMa metal; or (4) Any compound of a metal oxide in ruthenium; and (d) a mixture thereof. One embodiment of the invention relates to a structure comprising: (a) a thick film composition comprising: a) conductive silver; b) - or a plurality of flux materials; dispersed in c) an organic medium; (b) Or a plurality of semiconductor substrates; the thick film composition is formed on - or a plurality of semiconductor substrates, and wherein electrical contact is formed between the conductor silver and the one or more semiconductor substrates after firing. • In one embodiment, the flux material comprises - or a plurality of glass frits. • In the aspect of this embodiment, the wealth includes an insulating film. Another aspect relates to a semiconductor device comprising the structure, wherein the composition has been fired, wherein the firing removes the organic vehicle and sinters the silver and the builder material. The other-state is related to a solar cell including the structure. In the aspect of this embodiment, the thick film composition further comprises the addition of 135568.doc -8. 200937450. In another aspect, the additive is selected from the group consisting of: (a) a metal, wherein the metal is selected from the group consisting of Zn, Mg, Gd, Ce, Zr, Ti, Mn, Sn, RU, Co, Fe, Cu, and Cr; (8) selected from the group consisting of Zn, Mg, Gd, Ce, Zr, Ti, Mn,

Sn, Ru, Co, Fe, Cu and. a metal oxide of one or more of the metals; (0) any compound which produces a metal oxide of (b) after firing, and (d) a mixture thereof. In one embodiment, the additive is Zn〇 Or MgO. In one aspect of the embodiment, the glass frit comprises: 8-25% by weight of Bi2〇3, B2〇3' glass frit, and further comprising one or more selected from the group consisting of the following: Components: Si〇2, LA, Geh, and V205. In one aspect of this embodiment, the structure is suitable for use in fabricating photovoltaic devices. One embodiment of the present invention relates to a method of fabricating a semiconductor device. The method comprises the steps of: (a) providing one or more semiconductor substrates, one or more insulating films, and a thick film composition, wherein the thick film composition comprises: singular conductive silver, b) __ or a plurality of flux materials, dispersed (c) applying the insulating film to the semiconductor substrate, (c) applying the thick film composition to the insulating film on the semiconductor substrate, and (d) firing the semiconductor, insulating a film and a thick film composition, wherein the organic medium is removed after firing Sintering the silver and glass frit, and penetrated by the insulating film the thick film composition of ingredients. One embodiment of the invention is directed to a method of fabricating a semiconductor device. 135568.doc 200937450 The method comprises the steps of: (a) providing one or more semiconductor substrates, and a thick film composition, wherein the thick film composition comprises: a) conductive silver, b) one or more flux materials, dispersion In (c) an organic medium, (b) applying the thick ruthenium composition to the one or more semiconductor substrates' and (c) firing the semiconductor and thick film composition, wherein the fire is removed after firing An organic vehicle that sinters the silver and glass powder. [Embodiment] The present invention addresses the need for semiconductor compositions, semiconductor devices, methods of fabricating such semiconductor devices, and the like, having improved electrical performance. One embodiment of the invention is directed to a thick film conductor composition. In one aspect of this embodiment, the thick film conductor composition can include: a conductor powder, a flux material, and an organic medium. The flux material may comprise a mixture of glass frit or glass frit. The thick tantalum conductor compositions may also include additives. The thick film barrier composition can include other additives or components. One embodiment of the invention is directed to structures wherein the structures comprise a thick film conductor composition. In one aspect, the structure also includes one or more insulating films. In one aspect, the structure does not include an insulating film. In one aspect, the structure includes a semiconductor substrate. In one aspect, a thick film conductor composition can be formed on the one or more insulating films. In one aspect, a thick film conductor composition can be formed on the semiconductor substrate. In the aspect in which the thick film conductor composition can be formed on a semiconductor substrate, the structure may not contain a coated insulating film. In one embodiment, the thick film conductor composition can be printed on a substrate to form a 135568.doc -10-200937450 bus bar. These bus bars can be more than two bus bars. For example, the bus bars can be three or more bus bars. In addition to the busbars, the thick film conductor composition can be printed on a substrate to form a connecting line. These cables can be contacted - busbars. The connecting wires contacting the bus bar can be staggered between the connecting wires contacting the second bus bar. • In an exemplary embodiment, three bus bars can be flat on one substrate. The bus bars can have a rectangular shape. Both sides of the intermediate bus bar can be in contact with the connecting line. On each of the side busbars, only one side of the rectangle can be in contact with the ® (four) line. The connection line of the contact side bus bar can be interleaved with the connection line contacting the intermediate bus bar. For example, the connection line contacting one side bus bar may be interleaved with the connection line contacting the intermediate bus bar on one side, and the connection line contacting the other side bus bar may be in contact with the intermediate bus bar on the other side of the intermediate bus bar. The connecting lines are staggered. Figure 2A provides an illustrative diagram of one embodiment of the presence of two bus bars. The first bus bar 201 is in contact with the first set of connection lines 203. The second bus bar 2〇5 is in contact with the first set of connecting wires 2〇7. The first set of connection lines 2〇3 are interleaved with the second set of connection 'lines 207. Figure 2A provides an illustrative diagram of one embodiment of the presence of three bus bars. The first bus bar 209 is in contact with the first set of connecting wires 21, and the second bus bar 213 is in contact with the second group connecting wires 215 and the third group connecting wires 217. The second set of connecting lines 215 contact one side of the second bus bar 213; the third set of connecting lines contact the opposite side of the second bus bar 213. The third bus bar 2丨9 is in contact with the fourth group of connecting wires 221. The first set of connection lines 211 are in error with the second set of connection lines 21 5 . The third set of connection lines 217 are interleaved with the fourth set of connection lines 221. 135568.doc -11 · 200937450 In one embodiment, the busbars formed on the substrate may be composed of two busbars arranged in a parallel arrangement, the wires being formed perpendicular to the busbars and arranged in an alternating parallel line pattern. Alternatively, the bus bars can be three or more bus bars. In the case of two busbars, the center busbar can be used as a common connection between the busbars to each side of the parallel configuration. In this embodiment, the coverage area of the two bus bars can be adjusted to be about the same as in the case of using two bus bars. In the case of three bus bars, the vertical line is adjusted to a shorter size suitable for the spacing between the bus bar pairs. In one embodiment, the component of the thick film conductor composition is an electrically functional silver powder, a zinc-containing additive, and a lead-free glass powder dispersed in an organic medium. Other additives may include metals, metal oxides or any compound that produces such metal oxides during firing. These components are discussed below. No Units One embodiment of the present invention relates to thick film conductor compositions. In one aspect of this embodiment, the thick film conductor composition can include: a conductor material, a flux material, and an organic medium. The conductor material can include silver. In an embodiment, the conductor material can be a conductor powder. The flux material can include one or more glass frits. The glass frit can be lead free. The thick film conductor composition may also include, a + additive. The additive may be a metal/metal oxide additive selected from the group consisting of: (4) a metal selected from the group consisting of Zn, Mg, Gd, Ce, Zr Τι, Μη, Sn, Ru, c〇, Fe, (5) and. (8) selected from Zn,

Mg Gd, Ce, Zr, Ti, Mn, Sn, RU, C. , or a metal oxide of one or more of the metals of Fe, Cu and Cr; (4) any compound which is (b) an oxide after firing; and (d) a mixture thereof. Thick film conductor set I35568.doc -12· 200937450 The composition may include other components. As used herein, "busbar" means a common connection for collecting currents. In one embodiment, the busbars may be rectangular in shape. In one embodiment the 'bus bars can be parallel. As used herein, "flux material" means a substance used to promote melting, or a substance to be melted. In one embodiment, the melting may be carried out at or below a desired processing temperature to form a liquid phase. In one embodiment, the inorganic component of the present invention comprises: (1) an electrically functional silver powder, (2) a zinc-containing additive, (3) a lead-free glass frit; and optionally, other metals selected from the following: / metal oxide additive: (a) a metal, wherein the metal is selected from the group consisting of Zn, Gd, Ce, Zr, Ti, Mn, Sn, RU, C., Fe, Cu, and Cr; (8) is selected from the group consisting of Zn, Gd, and Ce , Zr, Ti, Mn, Sn,

a metal oxide of one or more of the metals of Ru, Co, Fe, Cu and Cr; (c) any compound which produces a metal oxide of (15) after firing; and (d) a mixture thereof. A. Conductive Functional Materials The conductive materials may include Ag, Cu, Pd, and mixtures thereof. In one embodiment, the electrically conductive particles are Ag. However, such embodiments are intended to be non-limiting. Embodiments that utilize other conductor materials are contemplated and contemplated. The silver may be in the form of granules, in powder form, in the form of flakes, in the form of spheres, mixtures thereof, and the like, provided in a colloidal suspension. The silver may be, for example, a silver metal, a silver alloy, or a mixture thereof. The silver may include silver oxide (Ag2〇) or a silver salt such as AgCh AgN03 or Ag〇〇CCH3 (silver acetate), silver linoleum (Ag3p〇4) or a mixture thereof. Any form of silver that is compatible with other thick film components can be used, 135,568.doc 13 200937450 and will be apparent to those skilled in the art. Silver can be any of various percentages of the composition of the thick film composition. In one non-limiting embodiment, the silver can be from about 70 angstroms per ounce to about 99% of the solids of the thick film composition. In another embodiment, the silver can be from about 70 wt% to about 85 wt% of the solids component of the thick film composition. In another embodiment, the silver can be from about 90% to about 99% by weight of the solid component of the thick film composition. In one embodiment, the solid portion of the thick film composition can include from about 8 〇 wt ° / 〇 to about 90 wt % silver particles and from about 1 wt % to about 1 〇 wt 〇 / 〇 silver flakes. In one embodiment, the solid portion of the thick film composition can include from about 75 wt% to about 90 wt% ruthenium/iridium silver particles and from about 1 wt% to about 1 〇 wt 〇/〇 silver flakes. In another embodiment, the solid portion of the thick film composition can comprise from about 75 wt% to about 9 wt% silver flakes and from about i wt% to about 1 wt wt/〇 colloidal silver. In another embodiment, the solid portion of the thick film composition can comprise from about 6 wt% to about 9 wt% silver powder or silver flakes and from about 1 wt% to about 2 wt% colloidal silver. In one embodiment, the thick film composition includes a function # that imparts suitable electrical functional properties to the composition. Thus, the force energy phase comprises an electrically functional powder dispersed in an organic medium that acts as a carrier for forming the functional phase of the composition. In one embodiment the composition can be applied to a substrate. In another embodiment, the group can be fired. The substrate and the substrate burn out the organic phase, activate the inorganic bonding phase and impart electrical functional properties. In one embodiment, the functional phase of the composition can be electrically conductive coated or uncoated silver particles. In an embodiment, the silver particles can be coated. In an embodiment, the silver may be coated with various materials such as phosphorus. In an embodiment 135568.doc 200937450, the silver particles may be at least partially coated with a surfactant. The surfactant can be selected from, but not limited to, stearic acid, palmitic acid, stearates, palmitates, and mixtures thereof. Other surfactants may be utilized including lauric acid, palmetto, oleic acid, stearic acid, citric acid, myristate M acid, and linoleic acid. The counter ion can be, but is not limited to, hydrogen, ammonium, sodium, potassium, and mixtures thereof. The particle size of silver is not subject to any particular limitation. In one embodiment, the average particle size is less than ίο microns; in another embodiment, the average particle size is less than 5 microns.

In one embodiment, the silver oxide can be dissolved in the glass during the glass melting/manufacturing process. B. Additives One embodiment of the present invention relates to thick film compositions that may contain additives. In one aspect of this embodiment, the additive can be a metal/metal oxide additive selected from the group consisting of: (a) a metal, wherein the metal is selected from the group consisting of

Mg, Gd, Ce, Zr, Ti, Mn, Sn, Ru, c〇, 仏, 仏 and heart; (b) selected from Zn, Mg, Gd, Ce, Zr, Ti, —, sn, Ru, c〇 : a metal oxide of - or more of the metals of Fe, Cu and bismuth; (4) any compound which produces a metal oxide of (b) after firing; and (in the case of the mixture, in the embodiment) The particle size is not subject to any particular limitation. In one embodiment, the average particle size may be less than 10 microns; in one embodiment the average particle size may be less than 5 microns. In an embodiment, the average particle size may be from . In other embodiments, the average particle size may be from 6 microns to Η microns. In the embodiment, the average particle size may be from (10) to (10) coffee. In the embodiment - the metal/metal oxide additive The particle size can range from 135568.doc -15- 200937450 m _) to 125 coffee. In one embodiment the metal/metal oxide additive may have a particle size in the range of from 7 nanometers (nm) to 1 〇〇 nmi. In the examples: 2 and 2 can be used in the present invention, and the average particle size range (d50) is from 7 nanometers (nm) to 125 nm. In an embodiment, the additive can be an additive. The terminological additive may, for example, be selected from the group consisting of (4) Zn, (b) a metal oxide of Zn, (4) any compound which produces a metal oxide of Zn after firing, and (d) a mixture thereof.

The zinc-containing additive is added, wherein the Zn〇 may have an average particle diameter in the range of from 1 nanometer to 10 micrometers. ^ may have an average particle size of from rice to 5 microns. In m, ZnO may have an average particle diameter of from 60 nm to 3 μm. In another embodiment, the zinc-containing additive can have an average particle size less than μηι. In particular, the zinc-containing additive may have an average particle size in the range of from 7 nm to less than (n). In another embodiment, a zinc-containing additive (e.g., Tn, zinc resinate, etc.) may be present in the total thick film composition in a range from 2 to 16 weight percent. In another embodiment, the zinc-containing additive may be present in a range from 4 to 12 weight percent of the total composition. In the embodiment, Ζη〇 may be present in the composition in a range from 2 to 10% by weight of the total composition. In an embodiment,

ZnO may be present in the range of from 4 to 8 weight percent of the total composition. In another embodiment, ZnO may be present in the range of from 5 to 7 weight percent of the total composition. In the embodiment, the additive may be a magnesium-containing additive. The town-containing additive may, for example, be selected from the group consisting of (4) Mg, (b) Mg metal oxides, (4) any compound which can produce 135568.doc -16 - 200937450 Mg metal oxide after firing, and (d) a mixture thereof. In one embodiment, the magnesium-containing additive & Mg 〇, wherein the Mg 〇 may have an average particle size in the range of from 10 nm to 10 μm. In another embodiment, the MgO may have an average particle diameter of from 40 nm to 5 microns. In another embodiment, MgO may have an average particle size of from 60 nanometers to 3 microns. In another embodiment, the Mg(R) may have an average particle size of from 1 micron to 1.7 microns. In another embodiment, the Mg(R) may have an average particle size of from 0.3 microns to 1.3 microns. In another embodiment, the town-containing additive may have an average particle diameter smaller than 〇1(d). In particular, the magnesium-containing additive may have an average particle diameter in the range of from 7 nm to 100 nm.

MgO may be present in the composition in a range from o.i to 1% by weight of the total composition. In one embodiment, Mg 存在 may be present in the range of from 5 to 5 weight percent of the total composition. In another embodiment, Mg〇 may be present in a range from 0.75 to 3 weight percent of the total composition. In another embodiment, the lock-containing additive (e.g., magnesium resinate, etc.) can be present in the total thick film composition in an amount ranging from 0.1 to 10 weight percent. In another embodiment, the magnesium-containing additive can be present in the range of from 5 to 5 weight percent of the total composition. In another embodiment, MgO may be present in the range of < 0,75 to 3 weight percent of the total composition. In another embodiment, the magnesium-containing additive can have an average particle size of less than 0.1 μϊη. In particular, the magnesium-containing additive may have an average particle diameter in the range of from 7 nm to 1 nm. In an embodiment, the additive may contain a mixture of additives. The additive may be a mixture of metal/metal oxide additives selected from the group consisting of: 135568.doc 200937450 (a) a metal wherein the metal is selected from the group consisting of

Zn, Mg, Gd, Ce, Zr, Ti,

Any compound of Mn, Sn, Ru, c〇, pe Ce, Zr, Ti, Mn, Sn, one or more metal oxides; and (d) a mixture thereof. Zn, Mg, Gd, ee can be produced after firing

Cu and Cr; (b) a metal selected from the group consisting of zn, Mg, Gd, Ru, Co, Fe, Cu, and Cr; (c) a metal oxygen which can be produced after firing (b)

Zr, Ti, Μη, Sn,

Ru C. Compounds of metal oxides of Fe, Cu or Cr include (but are not limited to

Resin, octoate, organofunctional units and the like. In an embodiment, the additive may comprise a mixture of ZnO and MgO. C. Glass frit as used herein, without error" means that no ship is added. In one embodiment, a minor error may be present in the composition, and if no (iv) is added, the composition may still be considered shipless. In the examples, the error-free composition may contain less than lead. In one embodiment, the lead-free composition may contain less than 3 paws of gold. Those skilled in the art will recognize that the term is not covered. A composition containing a relatively small amount of lead. In one embodiment, the lead-free composition may not only contain no lead, but may also be free of other toxic materials, including, for example, cd, Ni, and carcinogenic toxic materials. In one embodiment, The lead-free composition may contain less than 1 〇〇〇ppm of lead, less than 1000 ppmiCd, and less than 1000 ppni2Ni. In one embodiment, the error-free composition may contain traces of Cd and/or Ni; in one embodiment, Cd is not , Ni or a carcinogenic toxic material is added to the error-free composition. In one embodiment of the invention, the thick film composition can comprise a glass material. In one embodiment, the 'glass material can include one of three components or Many. Glass-forming materials, intermediate oxides And modifiers. Exemplary glass materials can be 135568.doc • 18- 200937450 ❹

It has a high bond coordination and a small ion size; the glass-forming material forms a bridged covalent bond upon heating and self-melting quenching. Exemplary glass forming materials include, but are not limited to, Si〇2, B2〇3, P2〇5, V2〇5, Ge02, and the like. Exemplary intermediate oxides include, but are not limited to, Ti〇2, Ta205, Nb2〇5, Zr02, Ce02, Sn〇2, Al2〇3, Hf02, and the like. As is known to those skilled in the art, intermediate oxides can be used in place of glass materials. Exemplary modifiers can have greater ionic properties and can be at the bond end. Beta modifiers can affect specific properties; for example, modifiers can result in, for example, a decrease in glass viscosity and/or a change in glass wetting properties. Exemplary modifiers include, but are not limited to, oxides such as alkali metal oxides, soil metal oxides, Pb 〇, Cu0, Cd0, Zn0, Bi2〇3, Ag2〇, Μο〇3, W〇 3 and its analogues. In one embodiment, the glass material can be selected by those skilled in the art to aid in the penetration of at least a portion of the oxide or nitride insulating layer. As described herein, this at least partial penetration can result in the formation of effective electrical contact with the tantalum surface of the photovoltaic device structure. The formulation component is not limited to being a glass material. In one embodiment of the invention, a glass frit composition (glass composition) is provided. Non-limiting examples of glass frit compositions are listed in the following table and are described herein. Other glass frit compositions are considered. It is important to note that the compositions listed in Table 1 are not limiting, as it is contemplated that a glass chemist may perform minor substitutions of other ingredients without substantially altering the properties of the glass compositions of the present invention. In this manner, substitution of glass formers such as 1% by weight of weights 2 > 2 〇 5 0-3, Ge 〇 2 〇 3, V 2 〇 5 〇 3 may be used individually or in combination to achieve similar performance. Also available is 135568.doc •19- 200937450 or Ο ❹ can be substituted with one of various intermediate oxides such as Ti〇2, Ta2〇5, Nb2〇5, Zr〇2, Ce〇2, Sn02... Other intermediate oxides present in the material (i.e., Al2〇3, Ce〇2, Sn〇2). It can be seen from the data that usually the higher Si〇2 content of the glass degrades the performance. Si02 is believed to increase the glass viscosity and reduce the glass wetting. Although not shown in the composition of Table 1, 'the effect of glass having zero SiCh is expected to be good, because other glass formers such as Ρζ〇5, Ge〇2, etc. can be used to replace the function of low content of Si〇2. The CaO, alkaline earth metal content may also be partially or completely replaced by other alkaline earth metal components such as SrO, BaO and Mg〇. An exemplary glass composition in weight percent of the total glass composition is shown in Table 1. In one embodiment, the glass composition seen in the examples comprises the following oxide components in the following composition ranges: Si〇2 〇.1_8, Al2〇3 〇_4, B2 by weight of the total glass composition. 〇3 825, Ca〇&,

Zn〇 0-42, Na2〇 〇_4, Li2〇 〇_3 5, shame 3 28 85, Ag2〇 〇 3,

Ce〇2 0-4.5, Sn〇2 〇·3.5, tons (10). In another embodiment, the glass composition comprises: 4_4.5 'Al2〇3 0.5-0.7 >Ω·> Ω 〇n ^ 2 3 9-1 1 , CaO 0.4- by weight percent of the total glass composition 0.6, ZnO ii 14, Na20 0.7-1.1, Bi, 〇% ^ Φ 2〇3 56-67, B% 4-13. In one embodiment, the glass may contain a small amount of B2〇3 or no b2〇3. The composition listed in ^ includes the ingredient as a good component.

To be an example of a non-limiting, non-limiting I ^ ^ ^ fluoride component. For example, a metafluoride compound can be used as an alternative to .7 F Α1ϋ 4. Order to replace. Non-limiting examples include .ZnF2, A1F3, and a fluoropolymer thereof. For example, 5, oxides can be used plus 135568.doc • 20. 200937450 Table 1: Glass composition number of glass components in weight percent of total glass composition (wt% total glass composition > Si02 AI2O3 B2O3 CaO ZnO Na2〇U2〇Bi2〇3 Ag2〇Ce02 Sn02 BiF3 Glass I 4.00 2.50 21.00 40.00 30.00 2.50 Glass II 4.00 3.00 24.00 31.00 35.00 3.00 Glass III 4.30 0.67 10.21 0.55 13.35 0.94 57.85 12.12 Glass IV 4.16 0.65 9.87 0.53 12.90 0.91 66.29 4.69 Glass V 7.11 2.13 8.38 0.53 12.03 69.82 Glass VI 5.00 2.00 15.00 0.50 2.00 3.00 70.00 2.50 Glass VII 4.00 13.00 3.00 1.00 75.00 4.00 Glass vm 2.00 18.00 0.50 75.00 2.50 2.00 Glass IX 1.50 14.90 1.00 1.00 81.50 0.10 Glass X 1.30 0.11 13.76 0.54 1.03 82.52 0.74玻璃 Glass powder suitable for use in the present invention includes ASF1100 and ASF1100B, which can be referred to from Asahi Glass Company. In one embodiment of the present invention, the glass powder (glass composition) may have an average particle diameter in the range of 0.5 to 1.5 μm. In another embodiment, the average particle size can be 0 In the range of 8-1.2 μηη. In one embodiment, the softening point of the glass frit (Ts: the second transition point of DTA) is in the range of 300-600 ° C. In one embodiment, the glass in the total composition The amount of powder may range from 0.5 to 4 wt ° / Torr of the total composition. In one embodiment, the glass composition is present in an amount from 1 to 3 weight percent of the total composition. In another embodiment, The glass composition is present in the range of from 1.5 to 2.5 weight percent of the total composition. The glasses described herein are made by conventional glass making techniques. The glass is prepared in an amount of from 500 to 1000 grams. The ingredients can be weighed and desired. The mixture is mixed and heated in a bottom loading furnace to form a melt in a platinum alloy crucible. As is well known in the art, heating to a peak temperature (1000 ° C - 1200 ° C) and 135568.doc -21 - 200937450 The melt completely becomes thicker and more homogeneous. The smelt glass is quenched between oppositely rolled steel rolls to form a ig_2g secret glass plate. The resulting glass plate was ground to form a powder having a volume distribution between 1 and 3 microns. In embodiments, one or more of the additives described herein may be included in the glass, such as ZnO, MgO, and the like. Glass powders containing - or multiple additives are suitable for use in the embodiments described herein.

In one embodiment, the glass frit may comprise Bi2〇3, b2〇3, 8-25% by weight of the total glass composition, and further comprising one or more components selected from the group consisting of: Si〇2 , p2〇5, Ge02 and V2〇5. In an embodiment, the glass frit may include one or more of Al2〇3, Ce〇2, Sn02&CaO. In one aspect of this embodiment, the amount of 'Al2〇3, Ce02, Sn02, and CaO, based on the weight percent of the total glass composition, can be 'J, at 6. In one aspect of this embodiment, the amount of Al2〇3, Ce02, Sn02, and CaO may be less than 1.5 based on the weight percent of the total glass composition. In one embodiment, the glass frit may include one or more of BiF3 and Bi203. In one aspect of this embodiment, the amount of BiF3 and Bi2〇3 may be less than 83 by weight of the total glass composition. In one aspect of this embodiment, the amount of BiF3 and Bi203 can be less than 72 based on the weight percent of the total glass composition. In one embodiment, the glass frit may include one or more of Na20, Li2, and AgzO. In one aspect of this embodiment, the amount of Na2〇, Li2〇, and α§2〇 may be less than 5 based on the weight percent of the total glass composition. In one aspect of this embodiment, based on the weight percent of the total glass composition, Na2〇, 135568.doc -22· 200937450

The amount of Li2〇 and Ag2〇 may be less than 2.0. In an embodiment, the glass frit may include one or more of Al2〇3, Si2〇2, and B2〇3. In one aspect of this embodiment, the amount of Si202, Al2〇3, and B2〇3 may be less than 31 based on the weight percent of the total glass composition. In an embodiment, the glass frit may include one or more of Bi2〇3, BiF3, Na2〇, . Li2〇, and AgzO. In one embodiment, the amount of (Bi2〇3+BiF3)/(Na2〇+Li2〇+Ag2〇) may be greater than 14 by weight percent of the total glass composition. G fluxing crucible material An embodiment of the invention relates to a composition comprising the structure and apparatus of the composition, and a method of making the same, wherein the composition comprises a fluxing material, in one embodiment The flux material may have properties similar to glass materials, such as having lower softening characteristics. For example, a compound such as an oxide or a dentate compound can be used. The compounds assist in penetrating the insulating layer in the structures described herein. Non-limiting examples of such compounds include materials that have been coated with an organic or inorganic barrier coating or that are encapsulated in the coating to prevent adverse reactions with the organic binder component of the paste medium. Non-limiting examples of such flux materials can include pbF2, BiF3, V2〇5, alkali metal oxides, and the like. In an embodiment, the flux material can include lead ruthenate (Pb2si〇4). In one aspect of this embodiment, 10 to 100 wt% of the flux material may be PbzSi〇4. In another aspect, 5 〇 _ 99 wt% of the flux material can be pb2sio4. In another aspect, the wt% of the (four) agent material may be PbjiO4. In an embodiment, the flux material can be pb2Si〇4. 135568.doc • 23· 200937450 In one embodiment, the flux material may comprise one or more components selected from the group consisting of: 4PbO-Si〇2, 2Pb0-SiO2, 5PbO-B203-SiO2, ZnPb03 And Zn2Pb〇4. In another embodiment, the builder material comprises one or more components selected from the group consisting of:

ZnF2, AgBi(P03)4, AgZnF3-AgF, LiZn(P03)3, Cu3B206, .CuPb2F6, CsPb(P03)3, 2PbO-B2〇3 and 4Pb0-B203. In one embodiment, the flux material may also include glass frit. In an embodiment, the flux material can be 0 543 ❻ wt 总 of the total conductor composition. In another embodiment, the co-solvent material may be from 1 to 7 wt%, based on the weight of the total conductor composition; in another embodiment, 丨5_5 wt%; in another embodiment, 2- 4 wt°/〇. In one embodiment of the composition comprising a fluxing material, the fluxing material can comprise glass frit. For example, the glass frit may be Ο-ΐ wt% of the total conductor composition. In one embodiment, the glass frit may be from 0.01 to 1 wt% of the total conductor composition. Glass Blending Art In one embodiment, one or more glass frit materials may be present in a thick film composition in the form of a hybrid. In one embodiment, the first frit material can be selected by those skilled in the art for its ability to rapidly digest the insulating layer; in addition, the frit material can have strong corrosive forces and low viscosity. In one embodiment, the second frit material can be designed to slowly blend with the first frit material while retarding chemical activity. The resulting knives that affect the insulation of the insulating layer, but do not erode the underlying emitter diffusion area (which may cause the tool flow) to be uncorroborated. The glass 135568.doc -24- 200937450 glass frit material can be characterized as having a diffuse p-n junction region sufficient to provide a stable viscosity of the fabrication window to remove the insulating layer without damaging the semiconductor substrate. In a non-limiting exemplary hybrid, the first glass frit material may be Si〇2 1.7 wt% > Zr〇2 0.5 wt% 'B203 12 wt%, Na2〇〇4 wt%, Li2〇0.8 wt% And Bi2〇3 84.6 wt% and the second glass frit material can be Si〇2 27 wt%, Zr02 4.1 wt%, Bi203 68.9 wt%. The ratio of the blend can be used to adjust the ratio of the pusher to the optimum performance of the thick film conductor paste under conditions known to those skilled in the art. © Analytical Glass Testing Several test methods can be used to characterize glass materials as candidates for use in optoelectronic Ag conductor formulations and are known to those skilled in the art. These measurements are differential thermal analysis (DTA) and Thermo-mechanical Analysis (TMA) for determining Tg and glass flow dynamics. As needed, many other characterization methods are available, such as expansion assays, thermogravimetric analysis, XRD, XRF, and icp. Inert gas tt firing In one embodiment, the processing of the photovoltaic unit is performed by using nitrogen or other inert gas to be fired in the prepared unit. The firing temperature is usually set so that the self-drying thick film paste can be burned out. Agent material or other organic material present. In an embodiment, the temperature may be between 300 and 525 degrees Celsius. The firing can be carried out in a belt furnace using a high transfer rate (for example between 4 〇 2 〇〇吋 / min). A variety of temperature zones are available to control the desired heat distribution. The number of zones can vary, for example, between 3 and 9 zones. The photovoltaic cell can be fired at a set temperature between 135568.doc •25·200937450, such as 650 C and 1000 C. The beta firing is not limited to this type of firing, and encompasses other fast known to those skilled in the art. Burning furnace design. D. Organic Medium The inorganic component can be mixed with an organic medium by mechanical mixing to form a viscous composition called "paste" having a consistency and rheology suitable for printing. Various inert adhesive materials can be used as Organic medium. The organic medium can be a medium in which the inorganic component can be dispersed with sufficient stability. The rheological properties of the medium must provide good coating properties to the composition, including: stable dispersion of solids, suitable for screen printing. Viscosity and thixotropy, suitable wettability of substrate and paste solids, good drying rate, and good firing properties. In embodiments of the invention, the organic vehicle used in the thick enamel composition of the present invention may be non-aqueous inert Liquid. Any of a variety of organic vehicles may be used, which may or may not contain thickeners, stabilizers, and/or other common additives. The organic medium may be a solution of the polymer in a solvent. In addition, such as a surfactant A small amount of the additive may be part of the organic medium. For this purpose, the most commonly used polymer is ethyl cellulose. Other examples of polymers include ethyl. Hydroxyethyl cellulose, wood rosin, a mixture of ethyl cellulose and a phenolic resin, a polymethacrylate of a lower alcohol, and a monobutyl ether of ethylene glycol monoacetate can also be used. The most widely used solvents found in film compositions are ester alcohols and hydrazines (such as alpha-rosinol or beta-rosinol) or with such as kerosene, dibutyl phthalate, butyl carbitol, butyl. a mixture of carbitol acetate, hexanediol, and other solvents of a high-boiling alcohol and an alcohol ester. In addition, a volatile liquid for promoting rapid hardening after being applied to a substrate may be included in 135568.doc • 26· 200937450 In the vehicle, various combinations of these solvents and other solvents are formulated to obtain the desired viscosity and volatility requirements. The polymer present in the organic medium is in the range of 8 wt% to 11 wt% of the total composition. The thick silver composition of the present invention is adjusted to a predetermined, screen printable viscosity by an organic medium. The ratio of the organic medium in the thick film composition to the inorganic component in the dispersion depends on the method of applying the paste and the use thereof. Depending on the type of organic medium, and It may vary. Typically the 'dispersion will contain 70-95 wt% of the inorganic component and 5% by weight of the organic medium (vehicle) to obtain good wetting. One embodiment of the invention relates to a thick a film composition, wherein the thick film composition comprises: (a) a conductive silver powder; (b) one or more glass frits; dispersed in (c) an organic medium; wherein the glass frit comprises: Bi2〇3, B2〇3 The total glass frit is 8_25 by weight _% and further comprises one or more components selected from the group consisting of: Si〇2, p2〇5, Ge〇2& v2〇5. In this embodiment In one aspect, the glass frit may be lead-free. In one aspect of this embodiment, the glass frit includes: 2〇3 28-85, B2〇3 8-25, and one or more of the following: Si02 0-8, p2〇5 〇_3, Ge〇2 〇-3, V205 0-3. In one aspect of this embodiment, the glass frit includes SiO 2 0.1-8. In one aspect of this embodiment, the glass frit may include one or more intermediate oxides. Exemplary intermediate oxides include, but are not limited to, Al2〇3, Ce〇2, Sn02, Ti02, Ta205, Nb2〇5, and Zr〇2. In one aspect of this embodiment, the glass frit may comprise a 135568.doc • 27· 200937450 or a plurality of alkaline earth metal components. Exemplary alkaline earth metal components include, but are not limited to, broad Ca 〇, Sr 〇, Ba 0, Mg 〇. In the embodiment, the glass powder comprises one or more components selected from the group consisting of: Zn 〇 , Na20, Li20, Ag02 and BiF3.

In one aspect of this embodiment, the composition may also include an additive. Exemplary additives include: a metal additive or a metal-containing additive, and wherein the metal additive or metal-containing additive forms an oxide under processing conditions. The additive can be a metal oxide additive. For example, the additive may be a metal oxide selected from one or more of Gd, Ce, Zr, Ti, Mn, Sn, RU, Co, Fe, (^ and ^ metal). One embodiment of the present invention The invention relates to a semiconductor device comprising a composition comprising: (a) a conductive silver powder; (b) one or more glass powders; dispersed in (c) an organic medium; wherein the glass powder comprises: Biz〇3, ΙΑ, 25 wt% of the total glass frit and further comprises - or a plurality of components selected from the group consisting of: sk) 2, p2 〇 5, Ge 〇 2 and V 2 〇 5. One aspect of this embodiment is directed to a solar cell including the semiconductor device. An embodiment of the invention relates to a structure comprising: (a) a thick film composition comprising: (a) a conductive silver powder; (b) - or a plurality of glass frits; dispersed in 0) an organic medium; 135568 .doc -28- 200937450 wherein the glass frit comprises: Bi2〇3, B2〇3, the weight percentage of the total glass frit, and the further step comprises one or more components selected from the group consisting of: Si〇 2. P2O5, Ge02 and V2〇5; and (b) an insulating film, wherein the thick tantalum composition is formed on the insulating film, and wherein a component of the thick film composition penetrates the insulating film after firing And removing the organic medium. Structure One embodiment of the present invention relates to a structure comprising a thick film composition and a substrate. In an embodiment, the substrate can be one or more insulating films. In an embodiment, the substrate can be a semiconductor substrate. In one embodiment, the structures described herein are applicable to the fabrication of photovoltaic devices. An embodiment of the invention relates to a semiconductor device comprising one or more of the structures described herein; an embodiment of the invention relates to a photovoltaic device comprising one or more of the structures described herein; One embodiment of the invention relates to a solar cell comprising one or more of the structures described herein; an embodiment of the invention relates to a solar panel comprising one or more of the structures described herein. One embodiment of the invention is directed to an electrode formed from a thick film composition. In one embodiment, the thick film composition has been fired to remove the organic vehicle and to sinter the silver and glass particles. One embodiment of the invention pertains to a semiconductor device that includes an electrode formed from a thick film composition. In one embodiment, the electrode is a front side electrode. One embodiment of the invention pertains to the structures described herein, wherein the structures also include a back electrode. 135568.doc -29- 200937450 One embodiment of the invention pertains to structures wherein the structures comprise a thick film conductor composition. In one aspect, the structure also includes one or more insulating films. In one aspect, the structure does not include an insulating film. In one aspect, the structure includes a semiconductor substrate. In one aspect, the thick film conductor composition can be formed on the one or more insulating films. In one aspect, the thick film conductor composition can be formed on the semiconductor substrate. In the aspect in which the thick film conductor composition can be formed on a semiconductor substrate, the structure may not contain an insulating film. © Thick germanium conductor and insulating film structure: One aspect of the present invention relates to a structure comprising a thick film conductor composition and or a plurality of insulating films. The thick film composition may comprise: (a) a conductive silver powder; (b) - or a plurality of glass frits; dispersed in c) an organic medium. In one embodiment, the glass frits are error free. In an embodiment, the thick film composition may also include an additive as described herein. The structure can also include a semiconductor substrate. In one embodiment of the invention, the organic vehicle can be removed after firing and the silver and glass frit are sintered. In another aspect of this embodiment, the conductor silver and frit mixture can penetrate the insulating film after firing. The thick film conductor composition can penetrate the insulating film after firing. This penetration can be partially penetrated. The penetration of the insulating germanium by the thick film conductor composition can result in electrical contact between the conductor of the thick film composition and the semiconductor substrate. The thick film conductor composition can be printed on the insulating film. This printing can result in the formation of bus bars and connecting lines, for example as described herein. The printing of thick enamel can be carried out by, for example, electroplating, extrusion, ink jet, forming or multiplex printing or bringing. 135568.doc 200937450 Laminar gas fossils may be present on the insulating film. Nitridation can be deposited by chemical methods. The deposition method can be CVD, PCVD or other methods known to those skilled in the art. Insulating crucible In an embodiment of the present invention, the insulating film may include one or more components selected from the group consisting of titanium oxide, hafnium nitride, SiNx:H, antimony oxide, and cerium oxide/titanium oxide. In an embodiment of the invention, the insulating film may be an anti-reflective coating (anU-reflecti〇n c〇ating 'arC). In an embodiment of the invention, the insulating film may be coated; the insulating film may be coated on the semiconductor substrate. In an embodiment of the invention, the insulating film may be formed naturally, such as in the case of yttrium oxide. In an embodiment, the structure may not include an already coated insulating film, but may contain a naturally occurring substance such as yttria, which functions as an insulating film. Thick Film Conductor and Semiconductor Substrate Structure: One aspect of the present invention relates to a structure comprising a thick film conductor composition and a semiconductor substrate. In an embodiment, the structure may not include an insulating film. In an embodiment, the structure may not include an insulating film that has been applied to the semiconductor substrate. In one embodiment, the surface of the semiconductor substrate may include a naturally occurring substance such as Si〇2. In one aspect of this embodiment, the naturally occurring material (such as Si〇2) may have insulating properties. The thick film conductor composition can be printed on the semiconductor substrate in a pattern. This printing can result in the formation of, for example, bus bars and connecting lines as described herein. Electrical contact can be formed between the conductor of the thick film composition and the semiconductor substrate. A layer of tantalum nitride may be present on the semiconductor substrate. It can be deposited by chemical methods. 135568.doc •31 · 200937450 Tantalum nitride. The deposition method can be CVD, PCVD or other methods known to those skilled in the art. The structure of the tantalum nitride which can be chemically treated. One embodiment of the present invention relates to a structure in which the nitride layer of the insulating layer can be treated to cause removal of at least a portion of the tantalum nitride. This treatment can be a chemical treatment. Removal of at least a portion of the tantalum nitride can result in improved electrical contact between the conductor of the thick film composition and the semiconductor substrate. The structure can have improved efficiency. In one aspect of this embodiment, the tantalum nitride of the insulating film may be part of an anti-reflective coating (ARC). The tantalum nitride may be formed naturally or, for example, by chemical deposition. This chemical deposition can be performed by, for example, CVD or PCVD. Structure of Thick Film Composition Included Flux Material Not Glass Powder One embodiment of the present invention relates to a structure comprising a thick film composition and one or more insulating films 'where the thick film composition comprises conductive silver powder And one or more co-solvent materials and an organic medium, and wherein the structure further comprises three or more insulating films. In one aspect of this embodiment, the flux materials are lead free. In one aspect, the flux material is not glass frit. In one embodiment, the structure can further include a semiconductor substrate. The thick film conductor composition can penetrate the insulating film after firing. This penetration may be for example, for example, the surface of the insulating film may be penetrated by a thick tantalum conductor composition. The penetration of the insulating film by the thick film conductor composition can result in electrical contact between the conductor of the thick film composition and the semiconductor substrate. In one embodiment of the invention, a method and structure are provided in which a -conductor has been applied directly to a semiconductor substrate. In one aspect of this embodiment 135568.doc • 32-200937450, a mask can be applied to the semiconductor substrate in a pattern associated with the pattern of the conductor. An insulating layer can then be applied and the mask removed. The conductor composition can then be applied to the semiconductor substrate in a pattern associated with the area from which the mask is removed. One embodiment of the invention is directed to a semiconductor device comprising a composition wherein the composition comprises: a conductive silver powder prior to firing;

One or more glass frits, wherein the glass frit is lead-free; dispersed in an organic medium. In one aspect of this embodiment, the composition can include an additive. Exemplary additives are described herein. One aspect of this embodiment is directed to a solar cell including the semiconductor device. One aspect of this embodiment is directed to a solar panel including the solar cell. Bus Bars In one embodiment, a thick film conductor composition can be printed on a substrate to form a bus bar. These bus bars can be more than two bus bars. For example, the bus bars can be three or more bus bars. In addition to the busbars, the thick film conductor composition can be printed on a substrate to form a connecting line. These cables can be in contact with a bus. The connecting wires contacting the bus bar can be staggered between the connecting wires contacting the second bus bar. In an exemplary embodiment, the three bus bars can be parallel to each other on a substrate. The g rows can have a rectangular shape. The longer sides of the intermediate bus bar can be in contact with the connecting wires. On each of the side bus bars, only one side of the longer rectangle can be in contact with the connecting line. The connection line on the contact side busbar can be interleaved with the connection line between the contact busbars in contact with a side busbar 135568.doc -33- 200937450. For example, the cable can be staggered with the in-between and the _敎 connecting lines, and the other side s stream can be interlaced with the connecting line of the intermediate bus in the side of the towel. 2A provides an illustrative diagram of an embodiment in which two bus bars are present. The first bus bar 201 is in contact with the first set of connection lines 203. The second bus bar 2〇5 is in contact with the second set of connection lines 207. The first set of connecting lines 2〇3 are interleaved with the second set of connecting lines 207.

2B provides an illustrative diagram of an embodiment in which three bus bars are present. The first bus bar 209 is in contact with the first set of connection lines 211. The second bus bar 213 is in contact with the second set of connection lines 215 and the second set of connection lines 21 7 . The second set of connecting lines 215 contact one side of the second bus bar 213; the third set of connecting lines 217 contact the opposite side of the second bus bar 213. The third bus bar 2丨9 is in contact with the fourth group of connecting wires 221. The first set of connection lines 211 are interleaved with the second set of connection lines 215. The third set of connection lines 217 are interleaved with the fourth set of connection lines 221. Description of a Method of Making a Semi-Conductive Device A method of the present invention relates to a method of fabricating a semiconductor device. One aspect of this embodiment includes the following steps: (a) providing a semiconductor substrate, one or more insulating films, and a thick film composition 'wherein the thick film composition comprises: a) conductive silver powder, b) - or a plurality The glass frit is dispersed in c) an organic medium, (b) one or more insulating films are coated on the semiconductor substrate, (c) the thick film composition is applied to the one or more insulating layers of the semiconductor substrate On the film, and 135568.doc -34- 200937450 (d) firing the semiconductor, one or more insulating films and a thick film composition, wherein the organic medium is removed after firing, and the silver and glass frit are sintered, And the edge is penetrated by the component of the thick film composition. In one aspect of this embodiment, the glass frit may be free of lead. In one aspect of this embodiment, the one or more insulating films may optionally include a group of the following: a tantalum nitride film, a titanium oxide film, a SiNx:H film, a hafnium oxide film, and a hafnium oxide/titanium oxide film. membrane. Ο 之一 An embodiment of the invention pertains to a semiconductor device formed by the method described herein. One embodiment of the invention is directed to a solar cell comprising a semiconductor device formed by the methods described herein. One embodiment of the invention is directed to a solar cell comprising an electrode comprising silver powder and one or more glass frits, wherein the glass frit does not contain lead. One embodiment of the present invention provides a novel composition that can be used to fabricate semiconductor devices. The semiconductor device can be fabricated from a structural element consisting of a bonded semiconductor substrate and a tantalum nitride insulating film formed on one of its major surfaces. The method of manufacturing a semiconductor device includes the steps of: coating a thick material composition of the present invention having a capability of penetrating an insulating film in a predetermined shape and at a predetermined position, for example, coating and printing on an insulating crucible, followed by firing The conductive thick film composition is melted and passed through the insulating film to achieve electrical contact with the stone substrate. In an embodiment, the electrically conductive thick film composition can be a thick film paste composition, as described herein, having a zinc additive, having 3 Å. . ·. . The softening point of the glass === mixture (dispersed in an organic vehicle) and, where appropriate, other metal/metal oxide additives. 135568.doc -35 · 200937450 In embodiments, the composition may include a glass powder content of less than $% by weight of the total composition and up to 6% by weight of the total composition with optional other metal/metal oxide additives The combined content of the additive. Embodiments of the present invention also provide a semiconductor device fabricated by the method. In the embodiment of the present month, a nitride film or an oxide film may be used as the insulating film. The nitride film may be deposited by electro-chemical vapor deposition (eg, flow & 1 • ν - Γ - Siti0n ' (4) Or formed by a thermal CVD method. In one embodiment, the oxide 7 film can be formed by thermal oxidation, thermal CFD or electropolymerization CFD. In an embodiment, the method of fabricating a semiconductor device may be characterized by fabricating a semiconductor device from a structural component, the structural component comprising a bonded semiconductor substrate and an insulating film formed on a major surface thereof, wherein The insulating layer is selected from the group consisting of titanium oxide, tantalum nitride, SiNx:H, cerium oxide, and cerium oxide/titanium oxide film, the method comprising the steps of: a metal paste material having the ability to react with the insulating film and penetrate the insulating film The predetermined shape is formed on the insulating film at a predetermined position to form electrical contact with the ruthenium substrate. The titanium oxide film can be formed by applying a titanium-containing organic liquid material onto the semiconductor substrate and firing it, or by thermal CVD. In one embodiment, the tantalum nitride film can be formed by PECVD (plasma enhanced chemical vapor deposition). An embodiment of the present invention also provides a semiconductor device manufactured by the same method. In an embodiment of the present invention, an electrode formed of the conductive thick film composition of the present invention may be in an atmosphere composed of a mixed gas of oxygen and nitrogen. Boiled under. This firing method removes the organic medium and sinters the glass frit 135568.doc -36-200937450 and Ag powder in the conductor thick film composition. The semiconductor substrate can be, for example, a single crystal or a polycrystalline germanium. Figure 1 (a) does not provide a step of a substrate having an engraved surface that reduces light reflection. In one embodiment, a single crystal germanium or polycrystalline germanium semiconductor substrate is provided. In the case of a solar cell, the substrate can be cut from an ingot formed by a pulling or casting method. Removal by a tool such as a wire saw for cutting can be performed by using an aqueous alkali solution such as an aqueous solution of potassium hydride or an aqueous solution of sodium hydroxide or using a mixture of hydrofluoric acid and nitric acid to etch away about 10 μΐη〇μηη of the surface of the substrate. The substrate surface is damaged and contaminated by the wafer cutting step. Alternatively, a step of washing the substrate with a mixture of hydrochloric acid and hydrogen peroxide may be added to remove heavy metals (such as iron) adhered to the surface of the substrate. Thereafter, an anti-reflective engraved surface is sometimes formed using, for example, an aqueous alkali solution such as an aqueous potassium hydroxide solution or an aqueous sodium hydroxide solution. This produces a substrate 1 〇. Next, referring to Fig. 1(b), when the substrate used is a 卩-type substrate, an n-type layer is formed to produce a ρ_η junction. The method for forming the n-type layer may be the use of phosphorus helium (phosphorus (PO) diffusion of POClj. In this case, the depth of the diffusion layer can be controlled by controlling the diffusion temperature and time, and usually at about 〇, 3 The layer formed in the thickness range of μιη to 0.5 μπι is formed in the figure by reference numeral 20. Next, the separation of ρ_η on the front and back sides can be performed by the method described in the background of the present invention. When a phosphorus-containing liquid coating material such as phosphotite glass (PSG) is applied to only one surface of a substrate by spin coating, and diffusion is achieved by annealing under suitable conditions' These steps are not always necessary. #然, when there is a risk of forming an n-type layer on the back side of the substrate, the degree of completion can be increased by utilizing the steps detailed in the background of the present invention. Doc •37- 200937450 Next, in Fig. 1(d), a tantalum nitride film or other insulating film includes SiN^H (that is, the insulating film contains hydrogen for passivation during subsequent firing processing), oxidation a titanium film and a yttrium oxide film 30, which are formed in one The anti-reflective coating on the above-mentioned type 11 diffusion layer 20. The tantalum nitride film 3 reduces the surface reflectance of the solar cell to the incident light, thereby making it possible to greatly increase the generated current. The thickness depends on the refractive index thereof, although a thickness of about 700 A to 900 A is suitable for a refractive index of about 19 to 2. The tantalum nitride film can be formed by a method such as low pressure CVD, plasma CVD or thermal CVD. When thermal CVD is used, the starting materials are often dioxane (SiChH2) and ammonia (NH〇, and the film formation is carried out at a temperature of at least 7 〇 < rc. When using thermal CVD, the starting gas Thermal cracking at elevated temperatures results in the substantial absence of hydrogen in the tantalum nitride film, resulting in a composition ratio of Si3N4 between the hafnium and the nitrogen, which is generally stoichiometric. The refractive index falls within the range of substantially 1.96 to 1.98. Therefore, this type of tantalum nitride film is an extremely dense film, and its characteristics such as thickness and refractive index remain unchanged even when subjected to heat treatment in the subsequent step. When film formation is performed by plasma Cvd, it is used. The starting gas is usually a gas of SiA and NH3. The starting gas is decomposed by the plasma, and the film is formed at a temperature of 300 Å to 55 Å. (Because the film formation by the plasma CVD method is performed at a temperature lower than that of thermal CVD' Therefore, hydrogen in the starting gas is also present in the obtained tantalum nitride film. Also, since gas decomposition is achieved by plasma, another distinguishing feature of this method is the ability to greatly change the composition ratio between niobium and nitrogen. Specifically, by changing the ratio of the flow rate of the starting gas and the pressure and temperature during the film formation, the composition ratio between yttrium, nitrogen and hydrogen can be formed 135568.doc -38 - 200937450 different and refractive index A tantalum nitride film in the range of 1,8 to 2.5. When a film having such properties is heat-treated in a subsequent step, the refractive index may change before and after film formation due to effects such as hydrogen elimination in the electrode firing step. In such cases, the tantalum nitride film required for the solar cell can be obtained by first selecting the film formation conditions after considering the change in film quality which will occur due to the heat treatment in the subsequent step. In Fig. 1(d), a titanium oxide film may be formed on the ???type diffusion layer 2 to replace the tantalum nitride film 30, which functions as an anti-reflection coating. By coating a titanium-containing organic liquid material on η The titanium oxide film is formed by firing on the type diffusion layer 20 or by heat cvd. In Fig. 1(d), it is also possible to form a hafnium oxide film on the n-type diffusion layer 2 to replace the tantalum nitride film. 30. It functions as an antireflection layer. The tantalum oxide film is formed by thermal oxidation, thermal CVD or plasma CVD. Next, it is formed by steps similar to those shown in Figs. 1(e) and (f). The electrode, that is, as shown in Fig. 1(e), the aluminum paste 6 〇 and the back silver paste 7 丝网 are screen printed on the back surface of the substrate 1 as shown in Fig. He) and then dried. In the same manner as the back surface of the substrate, the front electrode is formed by silver paste screen printing on the tantalum nitride film 30, followed by drying and firing in an infrared oven; the set point temperature can be 70 (TC to 975 ° C, A period of from one minute to more than ten minutes, while a mixed gas stream of oxygen and nitrogen is passed through the furnace. As shown in Figure 1 (f), aluminum is in the form of impurities during firing. The aluminum paste is diffused into the crucible substrate 10, thereby forming a P+ layer 40 containing a high aluminum dopant concentration on the back surface. The firing converts the dried aluminum paste 60 into an aluminum back electrode 61. Simultaneous firing of the back silver paste 70 , it becomes a silver back electrode 71. During the firing, the boundary between the back aluminum and the back silver adopts an alloy state, thereby achieving an electrical connection of 135568.doc -39·200937450. The area is occupied by an aluminum electrode, in part by: forming: Ρ + layer 40. At the same time, because it is impossible to solder to the electric, the silver or silver/aluminum back electrode is used as a solar cell for copper via a copper strip or the like. The electrodes are connected to each other on a limited area of the back surface. On the front side, the front electrode silver paste 500 of the present invention is composed of silver, a zinc-containing additive, a glass frit, an organic medium, and optionally a metal oxide, and can be burned. During the preparation process, it reacts with the nitrogen cut film 3G and passes through the nitride film to achieve electrical contact with the inner layer 20. The burn-through state, that is, the front electrode silver paste melts and passes through the nitride; The degree of film 3〇 depends on the product of nitriding Depending on the quality and thickness, the composition of the front electrode silver paste and the firing conditions, the conversion efficiency and moisture resistance reliability of the solar cell are significantly dependent on the burn-through state to a large extent. Examples The thick bismuth composition of the present invention is herein The following table 2_6 is shown. Paste preparation and σ paste preparation is done by the following procedure: weigh the appropriate amount of solvent, medium and surfactant, then mix in a mixing tank for 15 minutes, then add glass powder and metal additives and then Mix for 15 minutes. Since Ag is a major part of the solids of the present invention, it is added incrementally to ensure better wetting/swallowing. When fully mixed, the paste is repeated at a gradually increasing pressure of 〇pSi to 4 psi. Pass through a 3-roll mill. Adjust the gap between the rolls to 丨mil. The degree of dispersion was measured by fineness of grind (FOG). The FOG value may be equal to or less than 20/10 for the conductor. ASF1100 glass powder used in the following examples (available from Asahi Glass • 135568.doc -40- 200937450

Company) is not used as received. It was ground to 〇50 in the range of 5.5-0.7 μm before use. Test procedure - efficiency

A solar cell constructed in accordance with the method described above was placed in a commercial IV tester to measure efficiency (ST-1000). The Xe arc lamp in the IV tester simulates sunlight of known intensity and illuminates the front side of the cell. The tester uses a four-contact method to measure the current (1) and voltage (V) at approximately 400 load resistance settings to determine the battery curve. The fill factor (FF) and efficiency (Eff) are calculated from the I-V curve. The paste efficiency and fill factor values were normalized to the corresponding values obtained for batteries associated with the industry standard pvi45 (E I· du Pont de Nemours and Company). Test Procedure - Adhesion After firing, the solder ribbon (copper coated with 96 5 Sn/3.5 Ag) was soldered to the busbar printed on the front side of the battery. In one embodiment, reflow is achieved at 3651 for 5 seconds. The flux used was unactivated Alpha-100. The weld area is approximately 2 mm x 2 mm. The adhesion strength was obtained by pulling the tape to the surface of the battery at an angle of 9 。. The normalized adhesive strength was calculated to compare with the minimum adhesion value of 3 〇〇 g. Table 2: Effect of glass composition on thick film silver paste

Glass Π) No. 3 Glass I Glass II Glass M Glass IV Glass V

Normalized jfc rate 74^8 85.5 135568.doc 200937450 Glass 瑀 VI 1.8 6 50.7 69.3 8.0 61.1 Glass νπ 1.8 6 56.7 77.5 9.3 71.0 Glass VIII 1.8 6 67.2 91.8 12.0 91.6 Glass IX 1.8 6 70.0 100.0 12.8 97.7 Glass X 1.8 6 65.7 93.9 11.8 90.1 Control group I (PV145)* 73.2 100.0 13.1 100.0 Control group 70.0 100.0 13.1 100.0 II(PV145)*__________ *Control group I and control group II represent PV145, high-performance thick film combination containing glass powder with Pb , available from EI du Pont de Nemours and Company. The percentages of glass frit and ZnO given in Table 2 are given as a percentage of the total thick film composition. The thick film containing glasses III, IV, VIII and IX achieved particularly good contact with the solar cell, as evidenced by the good battery performance of the thick film paste compositions similar to Control I and Control II. Table 3: Effect of ZnO addition on thick film silver paste Addition % ASF 1100* Glass frit % Fill factor (°/〇) Normalized to PV145 Fill factor efficiency (%) Normalized to PV145 Efficiency None 0 1.8 29.6 38 , 8 3.3 23.9 ZnO 4 1.2 72.6 95.3 13.0 94.2 ZnO 4 2.4 71.2 93.4 13.3 96.4 ZnO 6 1.8 76.3 100.1.: 14.1 | '102.2 ZnO 8 1.2 76.4 Ιϋο.3 13.7 99.3 ZnO 8 2.4 75.8 99.5 13.9 100.7 PV145 control group 76.2 ' 100.0 13.8 100.0

*ASF1100 glass frit can be constructed from Asahi Glass Company The percentages of glass frits and additives given in Table 3 are given as a percentage of the total thick film composition. The thick film silver paste composition containing ZnO has superior electrical efficacy compared to the silver paste without ZnO. In the case of the addition of ZnO, the silver paste achieves an electrical performance similar to or better than that of -42-135568.doc 200937450 ^ ^ a ϋ, 1 dii ri ~ • u Pont de Nemours and Company. Table 4 _ Effect of various Zn additions on thick film silver paste Add % Add ASF 1100 Glass frit % Fill factor (%) Normalized to PV145 Fill factor efficiency (%) Normalized to PV145 efficiency ❺ No Zn ZnO powder ZnO powder resin zinc acid resin zinc silicate PV145 control group ο 6·4 2 6 1Λ 1Λ 1.8 1.8 1.8 1.8 1.2 29.6 74 74.3 72.4 67.9 69.3 73.3 40.4 101.0 101.4 98.8 92.6 94.5 100.0 3.3 13.2 12.5 12.7 12.1 11.8 12.9 25.6 102.3 96.9 98.4 93.8 91.5 100.0 The percentages of glass frits and additives given in Table 4 are given as a percentage of the total thick film composition. The experiments conducted and detailed in Table 4 illustrate the use of various types of inclusion additives and their effect on thick film compositions. Thick film silver paste compositions containing other forms and particle sizes of Zn and ZnO also achieve good electrical contact with Si solar cells. The zinc resinate used was 22% Zinc Hex-Cem, and its sound was from OMG (Cleveland, OH). Table 5: Effect of mixed oxide addition on thick silver paste Add Add % ASF 1100 frit %

ZnO+FeO 4/1-5 ZnO+Sn02 4.5/2-3 ZnO+GdO 4.5/1-5 PV145 control fill factor (%) 29.6 63.4 70.8 69.6 70.0 Normalized to PV145 fill factor 42.3 90.6 101.1 99.4 100.0 Efficiency 3.3 Π.4 13.2 12.7 13.1 The efficiency of normalization to PV145 25.2 87.0 100.8 96.9 100.0 The percentage of glass powder and additives given in Table 5 is the total weight of the 135568.doc -43- 200937450 W knife. Thick film silver paste combination containing a mixture of oxide frits J 'knife, net is not much improved performance. Table 6: Effect of other oxide addition on thick film silver paste Ο Adding no Ti02 〇2〇3 MnO MnO Mn〇2 FeO CoO Cu20 ZnO Zr02 M〇〇3 Ru〇2 Sn〇2 Sn〇2 W03 Ce〇2 GdO FeCoCrOx CoCrOx CuCrOx CuRu〇3 PV145 control group ο 666366666646694666666 Add % ASF 11001 Fill factor frit % (%) 1.8 29.6 1.8 53.4 1.8 55.5 1.8 26.8 1.8 33.3 1.8 28.7 1.8 59.4 1.8 50.6 1.8 44.4 1.8 72 1.8 30.5 1.8 25.8 1.8 34 1.8 58.4 1.8 58.9 1.8 52.3 1.8 54 1.8 62 1.8 61.2 1.8 38.2 1.8 59 1.8 54 71.1 Normalization is the fill factor efficiency of PV145 (%) ^ll·7·8·4·5·2·4·3·9·3· 8·1·8·6·9·2·1·7·0·9·0 L5·8·7·6·0·3·1·2·1·2·6·7·2·2·3 ·5·7·6·3·3·5·0· 4 7734487604348877885870 3 31 2161359684487 ··········♦· 9015208724159 •°·4·2·7 9·9·1°·1Λ 1Λ 6 5 7 °·9· 2. —1 11 Normalized to PV145 efficiency 26.0 72.4 79.5 12.6 40.2 18.1 82.7 70.1 59.8 100.8 34.6 11.0 45.7 76.4 79.5 70.9 74.088.2 84.3 44.9 83.5 74.8 100.0 135568.doc -44- 1 ASFll〇 Glass Powder available from Asahi Glass Company are given in Table 6 in the glass frit and the additive percentage given as a percentage of the total composition based thick film group. All of the oxide additions to the thick film silver paste detailed in the above table lead to improved solar cell performance. 200937450 Table 7: Effect of ZnO additive content on the adhesion of thick film silver paste to Si ASF1100 glass frit % ZnO % Adhesion (g) Normalized adhesion (%) 2· 4··8·2 11 Ί1 1Λ n /t\ νΊ V^ 5 6 4 3 8 5 4 4 3 2 6 5 7 11 1815141194 *ASF1100 glass powder is available from Asahi Glass Company. The percentage of glass powder and additives given in Table 7 is the total thick film combination. The weight percentage of the substance is given.

The magnesium-containing additive was evaluated using a 611-inch 20〇4]11 wafer from (^-匸6118) to evaluate the effect of MgO over a range of processing temperatures. The Ag content was 82%. Table 8: Efficiency processing of cells with MgO % added Set temperature MgO % 900°C 925〇C 950〇C Sample I 0 6.51 5.53 6.53 Sample 2 0.25 5.12 7.72 7.78 Sample 3 0.5 10.09 13.45 10.06 Sample 4 0.75 11.57 13.08 11.95 Sample 5 I 14.64 15.86 14.78 Sample 6 1.5 15.52 15.62 15.40 Sample 7 3 14.61 13.82 13.08 Sample 8 4 14.68 13.50 10.64 Table 9: Electrical effect of fired cell frit %% [MgO] [ZnO] Zone 4 Voc Efficiency % Fill factor % Isc Glass A 1.5 lO 925 595.8 14.24 70.49 8.25 Glass A 2.0 lO 925 598.4 15.25 74.67 8.30 Glass B 1.0 0.75 1.25 925 596.6 15.68 77.88 8.21 Glass B 1.0 lO lO 925 597.8 15.44 75.00 8.38 Glass B 1.0 1.25 0.75 925 598.1 13.95 69.28 8.10 I35568.doc -45- 200937450 Examples contain assistance The composition of the flux was prepared as shown in Table 10. A conductor composition (silver paste) containing a flux was used. The components are expressed in wt% of the total composition. A paste containing glass powder, silver and an organic vehicle; 8 barriers include a flux material, a paste of silver and an organic vehicle. The paste described in the B barrier includes glass powder. The flux material lead ruthenate (PbzSiO4) is used. Table 10 in the paste described in the column. Table 10 AB paste glass powder flux _ — (wt%) (wt %) silver 80 80 3.4 2,4 organic matter 16.6 17.6 total 100 100 examples based on the dissolution of silver paste Comparison based on glass :: for solar energy

Effect of Battery Efficiency The pastes A and B of Table 10 were used to form the front electrode of a solar cell, and were fabricated by the method described herein. Figure 3 illustrates the observed efficiency of the resulting solar cell. The efficiency of a solar cell using the paste A to form a front electrode is shown in the column called "Glass". The efficiency of a solar cell using the paste B to form a front electrode is shown in the column called "Fluidizer". BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1A to 1F are process flow diagrams illustrating the manufacture of a semiconductor device. The reference numerals shown in Figs. 1A to 1F are explained below. 135568.doc -46- 200937450 ίο : P-type germanium substrate 20 : n-type diffusion layer 30 : tantalum nitride film, titanium oxide film or hafnium oxide film 40 : ρ + layer (back surface field, BSF) 50 : formed on the front side Silver paste ' 51 : Silver front electrode (obtained by firing the front silver paste) . 60 : Ming paste on the back surface 61 : Ming back electrode (obtained by firing the back aluminum paste) © 70: Forming Silver or silver/name paste 71 on the back side: silver or silver/aluminum back electrode (obtained by firing the back silver paste) 80: solder layer 500. Silver paste 501 formed on the front side according to the present invention: according to the present Inventive Silver Front Electrode (Formed by Firing a Front Silver Paste) Figure 2A provides a top side view of an exemplary semiconductor in which a thick germanium conductor composition has been printed onto a substrate to form two busbars. Figure (5) provides a top side view of an exemplary semiconductor in which a thick film conductor composition has been printed on a substrate to form three bus bars. Figure 3 is a comparison of a flux-based silver paste with a corresponding glass-based paste. [Main component symbol description] 10 Ρ type 矽 substrate 20 η type diffusion layer 30 nitriding film, titanium oxide film or oxidized second film 135568.doc -47- 200937450

40 50 51 60 61 70 71 80 201 203 205 207 209 211 213 215 217 219 221 500 501 P+ layer (back surface field, BSF) Silver paste silver front electrode formed on the front side (obtained by firing the front silver paste) The aluminum paste formed on the back side is obtained on the back side of the electrode (obtained by firing the back aluminum paste) on the back side of the silver or silver/aluminum paste silver or silver/aluminum back electrode (obtained by firing the back side silver paste) Soldering layer first busbar first group connecting line second busbar second group connecting line first busbar first group connecting line second busbar second group connecting line third group connecting line third busbar fourth Group of silver wires formed on the front side according to the present invention. Silver front electrode according to the present invention (formed by firing a front silver paste) 135568.doc -48·

Claims (1)

200937450 X. Patent Application Scope 1. A conductor composition comprising: a) conductive silver; b) one or more flux materials; c) in an organic vehicle. Dispersed in e ❹ 2 • The composition of claim 1 contains Pb2Si〇4. 3. The composition of claim 1, wherein the composition comprises a fluxing material in an amount of from 0.5 to 13% by weight based on the weight of the conductor composition. 4. The composition of claim 3, wherein the composition comprises 1.5 to 5 wt% of a flux material by weight of the conductor composition. 5. The composition of claim 1 further comprising one or more conjugated additives. 6. The composition of claim 1 7. 0-1 wt% of the composition of claim 6. 8. A structure comprising: 0) a thick bismuth composition comprising: a) conductive silver; b) - or a plurality of flux materials; dispersed in c) an organic medium; (b) - or a plurality of insulating films Wherein the thick film composition is formed in the one or more to remove the organic medium after firing. Wherein at least one of the flux materials comprises one or more glass frits. Wherein the one or more glass frits are on the total combined insulating film, and 135568.doc 200937450. The structure of claim 8, wherein the one or more insulating films are penetrated by the components of the composition. For example, the structure of claim 8 further includes one or more semiconductor substrates. 11. The structure of claim 1 wherein the structure is a solar cell. 12. A method of fabricating a semiconductor device comprising the steps of: (a) providing one or more semiconductor substrates, one or more insulating films, and a thick film composition, wherein the thick film composition comprises: a) Conductive silver, b) - bismuth or a plurality of flux materials are dispersed in c) an organic medium, (b) applying the insulating film to the semiconductor substrate, (c) applying the thick film composition to the semiconductor substrate On the insulating film, and (d) firing the semiconductor, the insulating film and the thick film composition, wherein the organic vehicle is removed after firing, and the silver and the glass frit are sintered. ❿ 135568.doc